Compositions, textiles treated therewith, and processes for the treatment thereof



fabric is utimately desired.

condensates and bleached with chlorine.

United States Patent No Drawing. Application July 9, 1959, Ser. No. 825,885,

now Patent No. 3,002,859, dated Oct. 3, 1961, which is a continuation of application Ser. No. 517,062. June 21, 1955. Divided and this application June 28, 1960,

Ser. No. 39,228

'20 Claims. (Cl. 117139.4)

This invention relates to compositions for the treatment of textile materials, and it is particularly concerned with the treatment of textile materials of cellulosic type to improve their characteristics, especially to render the fabrics resistant to crushing and to shrinkage on laundering. It is also concerned with the treated fabrics thereby obtained and with methods for treating fabrics with the novel compositions. This application is a division of my copending application Serial No. 825,885, filed July 9, 1959, now U.S. Patent No. 3,002,859, issued Oct. 3, 1961, which is in turn a continuation of my application Serial No. 517,062, filed June 21, 1955, now U.S. Patent 2,901,463.

Heretofore, condensates of formaldehyde with melamine, urea, and cyclic urea derivatives, such as N,N'- ethyleneurea, and N,N-trimethyleneurea have been applied to cellulosic fabrics, such as cotton, for the purpose of imparting crush-resistance and reduced shrinkage on laundering. However, fabrics treated with these condensates pick up chlorine during bleaching operations using chlorine, such as those using i-t'in the form of a hypochlorite. On ironing the fabrics that have been bleached in this manner, severe discoloration and/ or loss in tensile and/or tear strengths have generally resulted. In those cases where severe discoloration is encountered, the treatment with these condensates is unsuitable when a white In some cases, as much as 90% loss in strength is encountered as a result of the action of heat as in ironing, on fabrics treated with these The presence on 'a fabric of a thermoset condensate of formaldehyde tion of the fabric on the mere treatment with a hypochlo- .rit'e bleach, unless care is taken to avoid excess chlorine and elevated temperatures. Ironing in such cases serves to aggravate the discoloration.

It has also been suggested, for crease-proofing cellulosic fabrics, to apply polymethylol tetrahydro-s-triazones substituted in the 5-position, such as dimethylol-S-methyltetrahydro-s-triazone-Z. However, fabrics treated therewith develop an unpleasant odor unless extreme care is taken to wash out by-products after the curing thereof on the fabrics. In addition, the fabrics treated therewith frequently show discoloration on heating or ironing whether or not the fabrics have been treated with chlorine before the heating or ironing is effected. The fabric leaves the curing stage in distinctly yellow condition. Heating after chlorination aggravates this yellowing severely.

It has been suggested in U.S. Patent 2,690,404 to combins a melamine-formaldehyde condensate with a diymethylol ethyleneurea in an etfort to reduce the discoloration and loss of strength of cellulosic fabrics treated with such condensates on bleaching and ironing. However, the

improvement obtained by this combination of condensates is generally relatively insignificant and the proportions in which the two condensates may be employed are quite narrow in range.

In accordance with the present invention, it has been discovered that eellulosic fabrics, such as cotton and the 3,043,718 Patented July 10, 1962 like, can be treated, to effect crease-proofing and so on without encountering serious odors, discoloration, and loss of strength, with an aqueous solution containing in certain proportions (l) a water-soluble condensate of formaldehyde with melamine (which will be termed hereinafter component A), with (2) a compound of Formula I following (which will be termed component B) where R is selected from the group consisting of 2-hydroxyethyl, 2-methyl-2-hydroxyethyl, and alkyl groups having 1 to 4 carbon atoms.

7 It has been found in accordance with the invention that the incorporation of at least 25 mole percent and not over mole percent of a compound of Formula I (component B) in a mixture comprising such compound and a watersoluble condensate of formaldehyde with melamine (component A) overcomes the disadvantages of discoloration and loss in strength of fabrics treated therewith that are normally encountered on heating after chlorination when melamine formaldehyde condensates are applied alone in accordance with the prior art. In addition, the odor normally associated with fabrics on which a triazone condensate has been cured is minimized. When less than 25 mole percent of the triazone condensate is employed, the improvements in respect to discoloration and loss of tensile strength are inappreciable; and when more than 75 mole percent is employed, the benefits in these factors are substantially reduced. For most purposes, from the stand point of cost, efliciency, freedom from discoloration, and low tensile loss on ironing or heating after chlorination, it is preferred to use from 30 to 50 mole percent of component B and from 70 to 50 mole percent respectively of component A.

Examples of the tetrahydro-s-triazones that may be em ployed include dimethylol-S-methyl-tetrahydro-s-triazone- 2, dimethylol-S-hydroxymethyl-tetrahydro-s-triazone-Z, di-

methylol-S-ethyl-tetrahydro-s-triazone-Z, dimethylol-S npropyl-tetrahydro-s-triazone-2, dimethylol-S isopropyl- 'tetrahydm-s-triazone-Z, dimethylol-S-t-butyl-tetrahydro-striazone-2, dimethylol-5-n-butyl-tetrahydro-s-triazone 2,

dirnethylol-5-sec-butyl-tetraihydro-s triazone 2. These methylol derivatives may be termed a dimethylol-tetrahydro-s-triazone-Z, and the condensate used may include the specific clear-cut compounds named or it may include a mixture of compounds containing the dimethylol compound. In any event, the formaldehyde condensates of this type may be obtained in known manner, such as by the condensation of a mixture of from 2 to 5 moles and preferably at least 2.5 moles of formaldehyde per mole of the tetrahydrotriazone in an aqueous solution thereof. The condensation may be eifected at a pH of 6 to 8 at a temperature of 30 to 120 C. and preferably between about to C. The extent of condensation and the completion of the desired reaction may be controlled by varying the time and temperature.

As component A, any water-soluble condensates of formaldehyde with melamine may be employed. An example of a specific compound that may be used includes trimethylolmelamine. In addition, the alkylated derivatives of the polymethylol melamine condensates obtained from the lower alcohols from methyl through butyl may be employed. Especially desirable results are obtained when highly methylolated melarnines and their methylated or ethylated derivatives are used such as pentacrease-resistant.

methylol-melamine, dimethoxymethyl-trimethylol-mela-' such condensates in a concentration in about 2 to 25% or more, based on total condensate solids. The particular concentration applied in any given instance may depend on the purpose for which the condensate mixture is applied and on the particular substrate or fabric to which it isapplied. In the case of cotton, the concentration is preferably 2 to 12%, whereas in application to rayon the concentration is preferably 5 to 20%, when the purpose of the application is to impart crease-resistance, crush- .resistance, or shrinkage stabilization.

While it is generally unnecessary, component A and component B may be reacted together provided any such reaction leaves the final condensate in a water-soluble condition. However, for most purposes, it is preferred not to co-react these components.

The solution containing the mixture of condensates (component A and component B) or the co-reacted condensates is stable when subjected to ordinary conditions of storage and can besold, shipped, and stored as such. Shortly before use, the acidic catalyst may be added, if

desired, as pointed out hereinafter.

An acidic catalyst is applied to the fabric either simultaneously with the condensates or before or after the mixture of condensates is applied. Preferably the acidic .catalyst is dissolvedin the aqueous solution of the mixture of condensates. Suitable catalysts include ammonium phosphate, ammonium thiocyanate, hydrochloric or other acid salts of a hydroxy aliphatic amine incling 2-methyl- 2 amino l propanol, 2-methyl-2-amino-1,3-propandiol, tris('hydroxymethyl)aminomethane, 2-phenyl-2 amino-lpropanol, 2-methyl-2-amino-1-pentanol, 2-aminobutanol,

'triethanolamine, 2-amino-2-ethyl-l butanol, also ammonium chloride, pyridine hydrochloride, benzyldimethylamine oxalate. The catalyst is generally introduced into the aqueous solution of the condensates at a concentration of about /2.% to 2% and preferably approximately 1%.

The compositions of the present invention may be applied to fibers, filaments, yarns, or fabricsof cellulosic typeand especially those of cotton or rayon for various purposes. For example,.they may be applied simply to modify :the feel or texture of the surface of the fabrics. When applied in greater quantities, the condensates of the present invention may be used to stiffen the fabrics and them Wrinkle-resistant, crush-resistant and The application of increasing amounts to make of the condensates serves to provide proportionately increased reduction in shrinkage of the treated fabric on laundering; and when about 3 to 8% by weight of the condensate, based on the weight of the fabric, is applied, the cellulosic fabric is generally substantially stabilized against shrinkage on laundering. The application of the condensates of the present invention may be employed for the purpose of aiding embossing operations. They may also be applied to fabrics as part of a process for their conversion to pliss fabrics.

The aqueous solution of the condensates may be applied by spraying, brushing, dipping, as in padding, or by rollercoating. After the application, excess may be removed, as by squeezing or squeegeeing. The treated fabric is then dried, such as by air-drying at room temperature or by the treatment'with heated air up to temperatures of about 212, F.

-After the fabric has been dried, the condensate mixture-is baked or cured on the fabric at a temperature of about 220 to 450 F. or higher, depending on the particular substrate. The time maybe varied generally in inverse proportions to the temperature. For example, the time may vary from about five seconds to half an hour. A time of 30 seconds at 400 F. is quite practical and a time of 15 to 30 minutes at 220 F. is generally satisfactory. The baking operation may simply be a continuation of the drying operation so that drying and curing may be effected in essentially a one-stage procedure.

The drying and/ or the baking may be effected by any suitable means for applying the heat, such as by the application of heated air currents, by infra-red radiation or by high frequency electric induction.

In the following examples which are illustrative of the invention, the parts are given by weight unless otherwise noted. The A.A.T.C.C. chlorination test referred to in the. examples involves the treatment with a hypochlorite solution containing 0.25% available chlorine at a temperature of 77 F.i2 F. for 15 minutes with intermittent stirring. This treatment is followed by rinses in six fresh water baths at 70 to 80 F. with a squeeze between rinses and drying in air at room temperature. The drying is followed by conditioning for at least four hours at 70 F. and 65% relative humidity. The percentage loss in tensile strength referred to hereinbelow is calculated by the formula o oe where t is the tensile strength after chlorination only and t is the tensile strength after both chlorination and ironing (or scorch test).

Example 1 A solution made up in water containing 2.5% of dimethylol-i(B-methyl-B-hydroxyethyl) tetrahydro -'striazone-Z and 3.5% of trimethylolmelamine and 0.5% of ammonium chloride. A bleached cotton fabric is padded through this solution. After draining excess and drying at 240 F. for five minutes, the fabric is cured at 300 F. for ten minutes. Chlorination is carried out under A.A.T.C.C. conditions above and the fabric is ironed at 365 F: 2 F. for 30 seconds (the standard A.A.T.C.C. scorch test). The ironed fabric is conditioned at 70 F. and 65 relative humidity for at least four hours before testing for strength. The creaseproofed fabric, after chlorination and ironing exhibits a slight discoloration and an approximately 29% loss of tensile strength and 0.5% of ammonium chloride. A bleached cotton fabric is padded through this solution. After draining excess and drying at 240 F. for five minutes, the fabric is cured at 300 F. for ten minutes. Chlorination is carried out under A.A.T.C.C. conditions above and the fabric is ironed at 365 F.:'2 for 30 seconds (the standard A.A.T.C.C. scorch test). The ironed fabric is conditionedat 70 F. and 65 relative humidity for at least four hours before testing for strength. The crease-proofed fabric, after chlorination and ironing exhibits a slight discoloration and an approximately 29% loss of tensile strength.

Example 2 (a) A solution is made up in water containing 2.5% of dimethylol-S-methyl tetrahydro S-triaZone-Z and 5% of trimethoxymethyl-dimethylol-melamine-and 0.5% by weight of the hydrochloride of 2-amino-2-methyl-propanol-l. A bleached cotton fabric is padded through this solution. After draining excess and drying at 240 F. for five minutes, the fabric is cured at 300 F. for ten minutes. Chlorination is carried out under A.A.T.C.C. conditions above and the fabric is ironed at 365 F.1- 2 F. for 3-0 seconds (the standard A.A.T.C.C. scorch test). The ironed fabric conditioned at 70 F. and 65% relative humidity for at least four hours before testing for strength. The fabric sufiered only about 15% loss in tensile strength; whereas when a fabric is treated in the same way with the same composition except that the triazone condensate is omitted and replaced by an additional quantity of the melamine condensate molarly equivalent to the triazone condensate replaced, the loss of tensile strength is about 40%.

(b) The procedure of part (a) hereof is repeated except that the concentration of the triazone derivative is increased to 3% and the concentration of the melamine derivative is decreased to 2.5%. Similar results are obtained.

Example 3 The procedure of Example 2(a) is followed except that the triazone is replaced with 2.0% of dimethylol-S-(fihydroxy-ethyl)-tetralhydro-ls-triazone-2 and the concentration of the trimethoxymethyl-dimethylol-melamine is 3.75%. The discoloration and loss in tensile strength after chlorination and ironing is comparable to those of Example 2(a).

I claim:

1. A composition comprising an aqueous solution of a mixture of 25 to 75 mole percent of a compound of the formula:

where R is selected from the group consisting of 2-hydroxyethyl, 2-methyl-2-hyd.roxyethyl, and alkyl groups having 1 to 4 carbon atoms, and 75 to 25 mole percent respectively of a water-soluble condensate of formaldehyde with melamine.

2. A composition comprising an aqueous solution containing a mixture of 25 to 75 mole percent of dimethylo l- 5-methyl-tetrahydro-s-triazone-2, and 75 to 25 mole percent respectively of a water-soluble condensate of formaldehyde With melamine.

3. A composition comprising an aqueous solution containing a mixture of 25 to 75 mole percent of dimethylol- 5-(,B-hydroxyethyl)-tetrahydro-s-triazone-2, and 75 to 25 mole percent respectively of a water-so1uble condensate of formaldehyde with melamine.

4. A composition comprising an aqueous solution containing a mixture of 25 to 75 mole percent of dimethylol- 5-ethyltetrahydro-s-triazone-2, and 75 to 25 mole percent respectively of a water-soluble condensate of formaldehyde with melamine.

5. A composition comprising an aqueous solution containing a mixture of 25 to 75 mole percent of dimethylol- 5 fl-methyl-fl-hydroxyethyl -tetrahydro-s-triazone-2, and 75 to 25 mole percent respectively of a Water-soluble condensate of formaldehyde with melamine.

6. A composition comprising an aqueous solution of a mixture of 25 to 75 mole percent of dimethylol-S-(fimethyl-fi-hydroxyethyl)tetralrydro-striazone-2, and 75 to 25 mole percent of trimethylol melamine.

7. A composition comprising an aqueous solution of a mixture of 25 to 75 mole percent of dimethylol-S- methyl-tetrahydro-s-triazone-2, and 75 to 25 mole percent of trimethoxymethyl dimethylobmelamine.

8. A composition comprising an aqueous solution of a mixture of 25 to 75 mole percent of dimethylo1-5-hydroxyethyl-tetrahydro-satrialone-2, and 75 to 25 mole percent of trimethoxy-methyl dimethylol-melamine.

9. A composition comprising an aqueous solution of a mixture of 30 to 50 mole percent of a compound of Formula I as defined in claim 1 and 70 to 50 mole percent respectively of a water-soluble condensate of formaldehyde with melamine.

10. A composition comprising an aqueous solution of a 6 mixture of 30 to 50 mole percent of dimethylol-S-(B- methyl-fi-lhydroxyethyl)-tetrahydro-s-triazone-2, and 70 to 50 mole percent of trimethylol melamine.

11. A composition comprising an aqueous solution of a mixture of 30 to 50 mole percent of dimethylol-S- methyl-tetra-hydro-s-triazone-2 and 70 to 50 mole percent of trimethoxymethyl dimethylol-melamine.

HO QHrN NCH2OH H2O Hz where R is selectedifrom the group consisting of 2-hydroxyethyl, 2.methy1-2-hydroxyethyl, and alkyl groups having 1 to 4 carbon atoms, and 75 to 25 mole percent respectively of a condensate of formaldehyde with melamine.

14. An article of manufacture comprising a cellulosic fabric modified by a reaction product of a mixture of 25 to 75 mole percent of dimethylol-5(B-methyl-fl-hydroxyethyl)-tetrahydro-s-triazone-2 and 75 to 25 mole percent respectively of trimethylol-melamine.

15. An article of manufacture comprising a cellulosic textile fabric modified by a reaction product of a mixture of 25 to 75 mole percent of dirnethylol-S-methyl-tetrahydro-s-triazone-Z and 75 to 25 mole percent respectively of trimethoxymethyl dimethylol-melamine.

16. An article of manufacture comprising a cellulosic textile fabric modified by a reaction product of a mixture of 25 to 75 mole percent of dimethylol-S-hydroxyethyltetrahydro-s-triazone-2, and 75 to 25 mole percent of trimethoxymethyl dimethylol'rnelamine.

17. A process for treating a fabric comprising applying to a cellulosic fabric an aqueous solution of a mixture of 25 to 75 mole percent of a compound of the formula:

HOCHzN NCHrOH where R is selected from the group consisting of 2-hydroxyethyl, 2-methyl-2-hydroxyethy-l, and alkyl groups having 1 to 4 carbon atoms, and 75 to 25 mole percent respectively of a Water-soluble condensate of form-aldehyde with melamine, and drying and curing the condensates on the treated fabric.

18. A'process for treating a fabric comprising applying to a cellulosic fabric an aqueous solution containing 2 to 25% of a mixture of condensates comprising 25 to 75 mole percent of dimethylol-S-(fl-methyl-fi-hydroxyethyl)- tetrahydro-s-triazone-Z, and 75 to 25 mole percent of trimethylol melamine, and drying and curing the condensates on the treated fabric at a temperature of 220 to 450 F.

19. A process for treating a fabnic comprising applying to a cellulosic fabric an aqueous solution containing 2 to 25% of a mixture of condensates comprising 25 to 75 mole percent of dimethylol-Smethyl tetrahydro-s-triazone-2 and 75 to 25 mole percent respectively of trimethoxymethyltdimethylol-melarnine, and drying and curcuring the condensates on the treated fabric at a temperaing the condensates on the treated fabric at a temperature ture of 220 to 450 F. of 220 to 450 F.

20. A process for treating a fabnic comprising applying References Ciied in the file of this Pawnt to a cellulosic fabric an aqueous solution containing 2 to UNITED STATES PATENTS 25% of a mixture of condensates comprising 25 to 75 mole percent of dimethylol-S-(B-hydroxyethyl) -tetrahy Egg i a1 23 .dro-s-triazpne-Z and 75 to 25 mole percent respectively of trimethoxymethyl dimethyiol-melamine, and drying and 2950553 Hurwitz 1960 

17. A PROCESS FOR TREATING A FABRIC COMPRISING APPLYING TO A CELLULOIS FABRIC AN AQUEOUS SOLUTION OF A MIXTURE OF 25 TO 75 MOLE PERCENT OF A COMPOUND OF THE FORMULA 